Light-sensitive silver halide color photographic material containing a mono-pyrazolone coupler and a bis-pyrazolone compound

ABSTRACT

COLOR STAINING OF CONVENTIONAL MONO-PYRAZOLONE MAGENTA COUPLERS IN PHOTOGRAPHIC MATERIALS IS PREVENTED BY USING, TOGETHER WITH THE MONO-PYRAZOLENE, A BIS-PYRAZOLONE IN AN AMOUNT OF 1-50% BY WEIGHT BASED ON THE MONO-PYRAZOLNE. THE BIS-PYRAZOLONE HAS THE FORMULA: F WHEREIN R IS ALKYL, ARYL OR SUBSTITUTED ARYL AND R&#39;&#39; IS HYDROGEN, ALKYL, ARYL, SUBSTITUTED ARYL OR A HETEROCYCLIC RADICAL WITH THE PROVISO THAT AT LEAST ONE OF R AND R&#39;&#39; CONTAINS AN ALIPHATIC HYDROCARBON RADICAL OF 12-20 CARBON ATOMS.

United States Patent 0,

3,556,799 LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIALCONTAINING A MONO-PYRAZOLONE COUPLER AND A BIS-PYRAZOLONE COMPOUNDToshihiko Yamamoto, Mitsuto Fujiwara, Tamotsu Kojima, and KenroSakamoto, Tokyo, Japan, assignors to Konishiroku Photo Industry Co.,Ltd., Tokyo, Japan No Drawing. Filed Sept. 11, 1967, Ser. No. 666,936Claims priority, application Japan, Sept. 19, 1966, 41/ 61,483 Int. Cl.G03c 1/40 US. Cl. 96-100 3 Claims ABSTRACT OF THE DISCLOSURE Colorstaining of conventional mono-pyrazolone magenta couplers inphotographic materials is prevented by using, together with themono-pyrazolone, a bis-pyrazolone in an amount of 1-50% by weight basedon the mono-pyrazolne. The bis-pyrazolone has the formula:

wherein R is alkyl, aryl or substituted aryl and R is hydrogen, alkyl,aryl, substituted aryl or a heterocyclic radi cal with the proviso thatat least one of R and R contains an aliphatic hydrocarbon radical of12-20 carbon atoms.

material useful in color photography. Particularly, the invention isconcerned with a light-sensitive, color photographic material to yield amagenta color image, which comprises a magenta coupler of themono-pyrazolone 3,556,799 Patented Jan. 19, 1971 "ice type, wherein abis-pyrazolone compound of the general formula wherein R is alkyl,non-substituted or substituted aryl, R

This invention relates to a light-sensitive photographic is hydrogen,alkyl, non-substituted or substituted aryl, or a heterocyclic radicalwith the proviso that a least one of R and R should contain an aliphatichydrocarbon radical having 12 to 20 carbon atoms is incorporated in thephotographic material. It is a principal object of the present inventionto provide a light-sensitive color photographic material which is freefrom color staining (magenta fog) during and color development.

As is well known, there are many magenta couplers which are capable offorming of magenta color image in a light-sensitive, color photographicmaterial. Among these, a magenta coupler of the mono-pyrazolone type cangive a stable color image with good tone quality at high speed. However,a photographic material in which the magenta coupler alone isincorporated is disadvantageous because it suffers from color stainingduring storage or development. Particularly, a magenta coupler of themono-pyrazolone type, the pyrazolone ring of which is substituted at the3-position with a long chain alkyl group, is very likely to cause colorstaining. Heretofore it was therefore necessary to use a magenta couplerof the monopyrazolone type in combination with an antifoggant(stabilizer) such as 2,4-di-tert. butyl hydroquinone, etc. However, theuse of such a stabilizer invariably causes a serious decrease in thesensitivity of high speed photographic emulsion.

In accordance with the present invention there is provided alight-sensitive, color photographic material which contains a magentacoupler of the mono-pyrazolone type which is completely prevented fromcolor staining while retaining all the advantages inherent in saidmagenta coupler.

Any compound of the pyrazolone type which is heretofore known may beused as the magenta coupler of the present invention. Typically usefulcompounds are the following:

(1) HzC C-Cuflas aw-Q 1-(3-a-su1iostearoylamldophenyl)3-phenyl-5-pyrazolone. N

-NHCO 0110 m,

5 coupler of the pyrazolone type as referred to above is used togetherwith a bis-pyrazolone compound of the above-indicated formula whichtypically may be the fol lowing:

4-bis-[l-phenyl-3-heptadecyl-5- pyrazolone].

4-bis-[1-(B-carboxylphenyD-B- heptadecyl-5-pyrazolone].

4-bis-[1-(4-su1io-pheny1)-3-heptadecy1-5- pyrazolone].

4-bis-[3-(4-wsulfopalmitoylamidophenyD-5-pyrazo1one].

C 0 O H y illolone] 4-bis-{l-pentadecyl-3-(4-carboxy- IphenyD-5-pyrazoloue].

4-bis-[l-(4-phenoxy-3-sulio-pl1enyl)-3- heptadecyl-S-pyrazolone].

These bis-pyrazolone compounds when used above (i.e. without addition ofa magenta coupler of the monopyrazolone type) will give a clear stablecolor image which may be increased in maximum color density because oftheir bimolecular coupling reaction. However, when they are used in ahigh speed, color photographic emulsion, they are inferior in couplingactivity and occasionally fail to give the desired photographic speed.

Such drawback of the bis-pyrazolone compounds as mentioned above can beavoided by jointly using the known mono-pyrazolone type magenta couplerin a lightsensitive, color photographic material. In accordance with theinvention there is thus provided a light-sensitive, color photographicmaterial which can give a stable color image with good tone quality atdesired high speed.

The required amount of the bis-pyrazolone compound to be added may varydepending on the type of magenta coupler of the mono-pyrazolone type andfurther on the type of bis-pyrazolone compound used but it usually willbe within the range of 150% by weight based on the weight of the magentacoupler. Incorporation of the specific compound of the bis-pyrazolonetype into a photographic material of the present invention can be madein the manner heretofore known per se in the art. For example, it ispossible to add the compound to a light-sensitive, color photographicemulsion containing a magenta coupler of the mono-pyrazolone type at anytime just before, during or after the second ripening of the saidemulsion. Addition of the bis-pyrazolone compound as a stabilizer forthe magenta coupler is most preferably made at the stage after thesecond ripening. Alternatively, the bis-pyrazolone compound may be addedto a starting material for the preparation of the emulsion, for examplegelatine. It is desirable to add the bispyrazolone compound in solutiondissolved in a suitable solvent, e.g. water, dilute alkali, methanol,ethanol, etc., if the addition is made to an emulsion.

Use of the bis-pyrazolone compound as a stabilizer does not adverselyinfluence the sensitivity of the color photographic emulsion concerned.The photographic emulsion containing the said bis-pyrazolone compoundcan be sensitized with a gold, sulfur or other chemical or opticalsensitizer.

As is well known to those skilled in the art, the term, alight-sensitive, color photographic emulsion or the like expression usedherein is to be understood to mean any conventionally knownlight-sensitive, color photographic emulsion which contains a magentacoupler of the mono-pyrazolone type. A suitable color photographicemulsion will be available with reference to Kagaku- Shashin-Binran(Manual of Photographic Science), vol. I, pp. 455-460 (Maruzen Co.,Tokyo, Japan).

The emulsion to which the bis-pyrazolone compound has been added can beapplied to a suitable support in the manner heretofore known per se inthe art, e.g. coating or pouring. Suitable supports include films,papers and glass plates. Particularly suitable are films of the types,such as cellulose esters, e.g. cellulose triacetate; polyesters obtainedby the polycondensation of phthalic, isophthalic or terephthalic acidwith a dihydric alcohol, e.g. polyethylene terephthalate,poly[cyc1ohexane-1,4-dimethylol]terephthalate, etc.', and polycarbonatesincluding those obtained by the polycondensation of bisphenyl A withcarbonic acid.

The present invention will now be explained in detail in conjunctionwith the following examples.

EXAMPLE 1 8 g. of the magenta coupler of the above-indicated Formula 1and 2 g. of the bis-pyrazolone compound of the above-indicated FormulaIX are dissolved in 35 ml. of l N sodium hydroxide. The resultingsolution is diluted with 400 ml. of water and then added to 1 kg. of agreen light-sensitive, high speed photographic gelatino-silveriodobromide emulsion. Then, the emulsion is adjusted to pH 7.0 andcoated on a cellulose acetate film support and dried. The thus obtainedfilm is exposed to green light and treated at 20 C. for 10 minutes witha color developer having the following formulation:

G. N,N-diethy1p-phenylenediamine sulfate 2.0 Sodium sulfite (anhydrous)2.0 Sodium carbonate monohydrate 82.0 Potassium bromide 2.0

Water to make up 1000 ml.

The treated film is then treated by stopping and fixing in the usualmanner. After rinsing for 10-20 minutes, this film was treated for 5minutes with a bleaching solution of the following formulation:

G. Potassium ferricyanide Potassium bromide 50 Water to make up 1000 ml.

Example 1. These control samples also are subjected to sensitometrictests.

The test results are set forth in Table 1.

In the above and also in Tables 2 and 3 which appear later, photographicspeed values are expressed as relative values based on the speed of thecontrol sample (1) which is rated as 100.

Separately, two sets of the above three film samples are stored underthe following condition:

Condition A.--For seven days at a temperature of 50 C. under a relativehumidity of 20%.

Condition B.For five days at a temperature of 55 C. under a relativehumidity of 80%.

After the specified storage, each set of the films are treated by colordevelopment in the same manner as before and then tested bysensitometry. The results are set forth in Table 2.

Color images obtained by using the samples of Example 1 are excellent intone quality and stability.

EXAMPLE 2 7 g. of the magenta coupler of the above-indicated Formula 7and 3 g. of the bis-pyrazolone compound of the above-indicated FormulaIV are dissolved in 30 ml. of 1 N sodium hydroxide. The resultingsolution is diluted with 500 ml. of water and added to 1 kg. of a greenlightsensitive gelatino-silver chlorobromide emulsion, which is thenadjusted to pH 6.9 with citric acid and coated on a. cellulose acetatefilm support. The resulting film is treated in the same manner as inExample 1 to obtain the results given in Table 3.

On the other hand, two control samples are prepared 10 by using in thecontrol sample 3 10 g. of the magenta coupler of the Formula 7 alone andin the contral sample 4 10 g. of the same magneta coupler and 500 mg. of2,4-di-tert. butyl hydroquinone. These control samples also are testedby sensitometry.

TAB LE 3 Photographic speed E Sample of Example 9 126 0. 02 Controlsample (3) 100 0. 07 Control sample (4) 85 0. 05

What we claim is:

1. A light-sensitive, color photographic material which comprises on asupport a light-sensitive gelatino-silver halide emulsion layercontaining a magenta coupler of the mono-pyrazolone type and abis-pyrazolone compound of the formula wherein R is alkyl, aryl orcarboxyl, sulfo or amido substituted aryl radical and R is hydrogen,alkyl, aryl, carboxyl, sulfo or amido substituted aryl or heterocyclicradical, with the proviso that at least one of said R and R contains analiphatic hydrocarbon radical having 1220 carbon atoms in an amountsui'ficient to prevent color staining with said magenta coupler.

2. A light-sensitive, color photographic material as claimed in claim 1,wherein said photographic material is a tricolor photographic film.

3. A light-sensitive, color photographic material as claimed in claim 1,wherein said bis-pyrazolone compound is present in the amount of l% byweight based on the weight of said magenta coupler.

References Cited UNITED STATES PATENTS 12/1946 Bauley 96100 12/1955Loria et a1. 9656

